US6504060B1 - Continuous process for the preparation of diaminodicyclohexylmethane - Google Patents
Continuous process for the preparation of diaminodicyclohexylmethane Download PDFInfo
- Publication number
- US6504060B1 US6504060B1 US10/122,769 US12276902A US6504060B1 US 6504060 B1 US6504060 B1 US 6504060B1 US 12276902 A US12276902 A US 12276902A US 6504060 B1 US6504060 B1 US 6504060B1
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- United States
- Prior art keywords
- process according
- catalyst
- reactor
- mda
- cascade
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a continuous process for the preparation of diaminodicyclohexylmethane (“PACM”) by hydrogenation of diaminodiphenylmethane (“MDA”) in the presence of a pulverulent catalyst.
- PAM diaminodicyclohexylmethane
- MDA diaminodiphenylmethane
- PACM is prepared industrially by hydrogenating MDA.
- PACM is used, for example, for the preparation of surface coatings, primarily as a precursor for the surface-coating raw material diisocyanatodicyclohexyl-methane.
- the isomer ratio is of particular importance for a number of applications.
- EP 639,403 A2 discloses a catalyst for the preparation of PACM with a low proportion of trans,trans isomer by hydrogenating MDA.
- This catalyst has a thin ruthenium- or rhodium-containing layer on a special support, namely a calcined or superficially rehydrated transition alumina, particularly hydragillite or bayerite.
- EP 639,403 A2 describes the deactivation of the catalyst by higher molecular weight constituents of the reaction mixture and the adjustment of a low proportion of trans,trans isomer in the product as a problem in the industrial preparation of PACM.
- the use of special catalysts is intended to solve these problems.
- the special catalyst is primarily suitable for use in reactors with a fixed catalyst bed in which the catalyst cannot be exchanged during operation.
- a large part of the reactor volume is occupied by the inactive core of the coated catalyst used and is no longer available as reaction volume.
- An object of the invention was therefore to provide a continuously operable process for the preparation of PACM with a low proportion of trans,trans4,4′-diaminodicyclohexylmethane characterized by a high space-time yield and a high catalyst service life.
- the invention provides a process for the preparation of diaminodicyclohexylmethane (“PACM”) with a proportion of trans,trans4,4′-diaminodicyclohexylmethane of from 17 to 24% comprising hydrogenating diaminodiphenylmethane (“MDA”) in the presence of a pulverulent catalyst in a continuously operated suspension reactor at a conversion of MDA of at least 95%, based on the amount of MDA.
- PAM diaminodicyclohexylmethane
- MDA diaminodiphenylmethane
- the conversion of MDA is preferably at least 99%, based on the amount of MDA used.
- the conversion can be influenced by measures known to the person skilled in the art, for example, by adjusting the residence time in the continuously operated suspension reactor.
- a cascade of two or more serially connected suspension reactors for example, a cascade of stirred-tank reactors or a cascade of bubble-columns.
- the MDA starting material is mixed with the pulverulent catalyst and the hydrogen required for the hydrogenation when using stirred-tank reactors as the suspension reactors by means of a stirrer and when using bubble-columns as suspension reactors by introducing hydrogen at high speed and generating a turbulent flow within the reactor.
- the pulverulent catalyst to be used according to the invention preferably comprises ruthenium, preferably 1 to 10% by weight (particularly preferably 4 to 8% by weight) of ruthenium.
- the ruthenium is preferably applied to a support in fine distribution in order to ensure good catalyst service life and good filterability.
- Suitable supports are, for example, aluminum oxides.
- the ruthenium is distributed largely homogeneously over the cross section of the support particles. This ensures that, upon mechanical stress within the reactor, no ruthenium particles are detached from the support, which is readily possible in the case of coated catalysts. Mechanical loading within the reactor sometimes results in breakage of the catalyst particles.
- a homogeneously impregnated catalyst does not produce a ruthenium-free surface but instead a fresh active ruthenium-containing catalyst surface.
- a catalyst in which the ruthenium is distributed largely homogeneously over the cross section of the support particles can be prepared, for example, by first allowing an aqueous solution of a ruthenium salt (e.g., ruthenium chloride or ruthenium nitrosilyl nitrate) to act upon an aluminum oxide powder and then precipitating out the ruthenium by adding a base (e.g., NaOH).
- a ruthenium salt e.g., ruthenium chloride or ruthenium nitrosilyl nitrate
- the catalyst is preferably used as a powder with an average diameter of the catalyst particles of from 5 to 150 ⁇ m, particularly preferably 10 to 120 ⁇ m, particularly preferably 30 to 100 ⁇ m.
- the catalyst can be used, for example, in an amount of from 1 to 10% by weight (preferably 3 to 8% by weight), based on the reaction mixture.
- the process according to the invention is carried out, for example, at a temperature of from 130 to 200° C., preferably from 140 to 190° C., particularly preferably from 150 to 180° C.
- the temperatures of the individual reactors can be different. It is advantageous to choose a temperature in the first reactor that is higher than that in the last reactor.
- the first reactor can be operated at 180° C., the second at 170° C., and the third at 150° C., for example.
- the hydrogen pressure is, for example, from 50 to 400 bar, preferably from 100 to 200 bar.
- Hydrogen is advantageously added in an excess of from 5 to 200%, preferably from 20 to 100%, of theory.
- the process according to the invention can be carried out with or without the addition of organic solvents.
- suitable solvents are alcohols, preferably secondary alcohols (e.g., isobutanol, cyclohexanol, or methylcyclohexanol) or tertiary alcohols (e.g., tert-butanol), particularly preferably tertiary alcohols.
- the solvent can be separated from the product by distillation and returned to the hydrogenation process.
- the proportion of water in the reaction mixture is preferably kept lower than 1% by weight, particularly preferably lower than 0.5% by weight.
- MDA diaminodiphenylmethane
- the parameters catalyst concentration, temperature, and residence time in the reactor can be used to adjust the content of trans,trans isomer in the product.
- products with a low proportion of trans,trans isomer, particularly with a proportion between 17 and 24%, can be achieved.
- the proportion of trans,trans isomer in the product can be adjusted by adapting the residence time of the reaction mixture in the reactor.
- the catalyst can be conveyed through the reactor or the reactor cascade together with the reaction mixture.
- the product mixture is then usually cooled, the excess hydrogen is removed, and the catalyst is filtered off.
- the catalyst is reused.
- catalyst activity decreases after a relatively long period of operation some of the catalyst can be removed from the system and replaced by fresh catalyst, meaning that a plant for carrying out the process according to the invention can be operated with constant average catalyst activity and constant throughput.
- the experiment was carried out in a continuously operated stirred tank reactor having a reaction volume of 330 ml.
- a pulverulent catalyst containing 5% by weight of ruthenium on an Al 2 O 3 support in a catalyst concentration of 5% by weight was introduced into the stirred-tank reactor.
- MDA was used in technical-grade quality (so-called MDA 90/10) with a proportion of about 10% of higher molecular weight components as a 33% strength by weight solution in isobutanol.
- the MDA 90/10-isobutanol mixture was metered into the reactor from a storage container.
- the reaction pressure was kept constant at 150 bar by continually replenishing hydrogen, and a temperature of 150° C. was set.
- the overflow of the reaction mixture passed into another container from which samples were taken for analysis.
- the samples were analyzed using gas chromatography.
- various average residence times were set.
- the residence time was set in one case so that the conversion of MDA, based on the amount of MDA used, was only 91.5%. In this case, the proportion of trans,trans isomer of the resulting PACM was below the desired range.
- Example 2 The experiment was carried out under the same conditions as in Example 1, but the residence time was shortened so that conversion was only partial. The product was then conveyed through the reactor two more times. The product corresponds to the product obtained in a cascade of three stirred-tank reactors.
- the experiment shows that when a cascade of three reactors is used, a very high conversion of MDA and a trans,trans proportion in the region of 20% can be simultaneously achieved and a high space-time yield is also achieved.
- the experiment was carried out in a discontinuously operated stirred-tank reactor having a reaction volume of 330 ml.
- a pulverulent catalyst comprising 5% by weight of ruthenium on an Al 2 O 3 support in a catalyst concentration of 5% by weight was introduced into the stirred-tank reactor.
- MDA was used in a technical-grade quality (so-called MDA 90/10) with a proportion of about 10% of higher molecular weight components as a 33% strength by weight solution in isobutanol.
- 330 ml of the MDA 90/10-isobutanol mixture were metered into the reactor from a storage container.
- the reactor pressure was kept constant at 150 bar by continually replenishing hydrogen, and a temperature of 150° C. was set.
- Samples were taken for analysis from the reaction mixture after various residence times of the reaction mixture in the reactor.
- the samples taken were analyzed using gas chromatography.
- the experiment shows that a product with a proportion of 20% trans,trans isomer can be obtained at a significantly lower space-time yield than for continuous hydrogenation in a cascade of three reactors.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10119135 | 2001-04-19 | ||
DE10119135A DE10119135A1 (de) | 2001-04-19 | 2001-04-19 | Kontinuierliches Verfahren zur Herstellung von Diaminodicyclohexylmethan |
DE10119135.9 | 2001-04-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020198409A1 US20020198409A1 (en) | 2002-12-26 |
US6504060B1 true US6504060B1 (en) | 2003-01-07 |
Family
ID=7681937
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/122,769 Expired - Fee Related US6504060B1 (en) | 2001-04-19 | 2002-04-15 | Continuous process for the preparation of diaminodicyclohexylmethane |
Country Status (4)
Country | Link |
---|---|
US (1) | US6504060B1 (fr) |
EP (1) | EP1251119A3 (fr) |
JP (1) | JP2002356461A (fr) |
DE (1) | DE10119135A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100292510A1 (en) * | 2008-01-18 | 2010-11-18 | Basf Se | Process for preparing cycloaliphatic amines |
US20110137083A1 (en) * | 2008-05-27 | 2011-06-09 | Basf Se | Continuous method and reactor for hydrogenating organic compounds |
US20120323041A1 (en) * | 2011-01-07 | 2012-12-20 | Ningbo Wanhua Polyurethanes Co., Ltd. | Method for Intermittently Producing 4,4'-Diaminodicyclohexylmethane with a Low Amount of the Trans-trans Isomer |
US11964259B2 (en) | 2019-12-31 | 2024-04-23 | Industrial Technology Research Institute | Catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives and method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives using the same |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10231119A1 (de) * | 2002-07-10 | 2004-02-05 | Degussa Ag | Verfahren zur Selektivitätserhöhung der Hydrierung von 4,4'-Diaminodiphenylmethan zu 4,4'-Diaminodicyclohexylmethan in Gegenwart eines N-Alkyl-4,4'-Diaminodiphenylmethans |
CN103265438B (zh) | 2013-05-22 | 2014-11-05 | 万华化学集团股份有限公司 | 二氨基二环己基甲烷的制备方法 |
TWI534131B (zh) | 2014-11-27 | 2016-05-21 | 財團法人工業技術研究院 | 氫化4,4’-二胺基二苯甲烷的觸媒與方法 |
CN109851508B (zh) * | 2018-12-25 | 2022-01-07 | 万华化学集团股份有限公司 | 合成低反反异构体含量和低焦油含量h12mda的方法 |
CN110756198A (zh) * | 2019-11-07 | 2020-02-07 | 西安凯立新材料股份有限公司 | 一种4,4′-二氨基二苯甲烷选择加氢用钌氧化铝催化剂及其制备方法与应用 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5578546A (en) | 1993-08-20 | 1996-11-26 | Huels Aktiengesellschaft | Catalyst for preparing bis-para-aminocyclohexylmethane containing a low proportion of trans/trans isomer by hydrogenation of methylenedianiline |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH515882A (de) * | 1965-12-23 | 1971-11-30 | Du Pont | Verfahren zur Herstellung von 4,4'-Methylen-di-(cyclohexylamin) |
DE2039818A1 (de) * | 1970-08-11 | 1972-02-17 | Basf Ag | Verfahren zur kontinuierlichen Herstellung von Bis(-aminocyclohexyl)-alkanen oder -aethern |
US4448995A (en) * | 1982-12-13 | 1984-05-15 | Mobay Chemical Corporation | Catalytic hydrogenation of di(4-aminophenyl)methane |
US4754070A (en) * | 1986-01-23 | 1988-06-28 | Air Products And Chemicals, Inc. | Hydrogenation of methylenedianiline to produce bis(para-aminocyclohexyl)methane |
ATE89260T1 (de) * | 1988-01-14 | 1993-05-15 | Huels Chemische Werke Ag | Verfahren zur produktion von 4,4'diaminodicyclohexylmethan mit niedrigem transtrans-isomergehalt durch katalytische hydrogenierung von 4,4'-diaminodiphenylmethan. |
-
2001
- 2001-04-19 DE DE10119135A patent/DE10119135A1/de not_active Withdrawn
-
2002
- 2002-04-08 EP EP02007355A patent/EP1251119A3/fr not_active Withdrawn
- 2002-04-12 JP JP2002110269A patent/JP2002356461A/ja not_active Withdrawn
- 2002-04-15 US US10/122,769 patent/US6504060B1/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5578546A (en) | 1993-08-20 | 1996-11-26 | Huels Aktiengesellschaft | Catalyst for preparing bis-para-aminocyclohexylmethane containing a low proportion of trans/trans isomer by hydrogenation of methylenedianiline |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100292510A1 (en) * | 2008-01-18 | 2010-11-18 | Basf Se | Process for preparing cycloaliphatic amines |
US8987517B2 (en) * | 2008-01-18 | 2015-03-24 | Basf Se | Process for preparing cycloaliphatic amines |
US20110137083A1 (en) * | 2008-05-27 | 2011-06-09 | Basf Se | Continuous method and reactor for hydrogenating organic compounds |
US20120323041A1 (en) * | 2011-01-07 | 2012-12-20 | Ningbo Wanhua Polyurethanes Co., Ltd. | Method for Intermittently Producing 4,4'-Diaminodicyclohexylmethane with a Low Amount of the Trans-trans Isomer |
US8759591B2 (en) * | 2011-01-07 | 2014-06-24 | Wanhua Chemical Group Co., Ltd. | Method for intermittently producing 4,4′-diaminodicyclohexylmethane with a low amount of the trans-trans isomer |
US11964259B2 (en) | 2019-12-31 | 2024-04-23 | Industrial Technology Research Institute | Catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives and method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives using the same |
Also Published As
Publication number | Publication date |
---|---|
JP2002356461A (ja) | 2002-12-13 |
US20020198409A1 (en) | 2002-12-26 |
EP1251119A3 (fr) | 2003-11-05 |
DE10119135A1 (de) | 2002-10-24 |
EP1251119A2 (fr) | 2002-10-23 |
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Owner name: BAYER AKTIENGESELLSCHAFT, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BUNNENBERG, ROLF;GROSCHL, ANDREAS;HOLZBRECHER, MICHAEL;AND OTHERS;REEL/FRAME:013083/0485;SIGNING DATES FROM 20020529 TO 20020617 |
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STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
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Effective date: 20110107 |